This application is a 371 of PCT/EP99/03676 filed May 27, 1999.
The present invention relates to a synergistically acting herbicidal mixture of a 3-heterocyclyl-substituted benzoyl derivative, a nitrogenous fertilizer and an adjuvant.
3-Heterocyclyl-substituted benzoyl derivatives are known and are described, for example, in WO 96/26206, WO 97/41116, WO 97/41117 and WO 97/41118.
Herbicidal compositions of substituted cyclohexanediones and nitrogen fertilizers are disclosed in EP-B-0584 227.
It is an object of the present invention to provide a herbicidal mixture which comprises 3-heterocyclyl-substituted benzoyl derivatives and whose herbicidal action exceeds the action of the pure active ingredient.
We have found that this object is achieved by a herbicidal mixture which comprises
a) a herbicidally active amount of a 3-heterocyclyl-substituted benzoyl derivative of the formula I 
xe2x80x83in which the variables have the following meanings:
R1,R2 are hydrogen, halogen, C1-C6-alkyl, C1-C6-alkylthio, C1-C6-alkylsulfinyl, C1-C6-alkylsulfonyl, C1-C6-haloalkyl, C1-C6-alkoxy, C1-C6-haloalkoxy;
R3 is hydrogen, halogen, C1-C6-alkyl;
X is a heterocycle from amongst the group consisting of isoxazolyl, 4,5-dihydroisoxazolyl and thiazolyl, it being possible for the heterocycle to be optionally monosubstituted or polysubstituted by halogen, C1-C6-alkyl, C1-C4-alkoxy, C1-C4-haloalkyl, C1-C4-haloalkoxy, C1-C4-alkylthio;
R4 is a pyrazole of the formula II 
xe2x80x83which is linked in the 4-position and where
R5 is hydrogen or C1-C6-alkyl,
R6 is C1-C6-alkyl or their environmentally compatible salts;
b) a nitrogenous fertilizer in a synergistically effective amount and
c) an adjuvant in a synergistically effective amount.
The herbicidal mixture according to the invention exhibits a synergistic effect and is selective for those crop plants which also tolerate the individual compounds themselves.
3-Heterocyclyl-substituted benzoyl derivatives of the formula Ib which are especially preferred with a view to the synergistic herbicidal action are those in which 
R1, R2 are chlorine, methyl, ethyl, SCH3, SOCH3, SO2CH3;
R3 is hydrogen and methyl;
R5 is hydrogen, methyl, trifluoromethyl;
R6 is methyl, ethyl, isopropyl;
X is a heterocycle from amongst the group: isoxazolyl, 4,5-dihydroisoxazolyl and thiazolyl, it being possible for the heterocycle to be optionally monosubstituted or polysubstituted by halogen, C1-C6-alkyl, C1-C4-alkoxy, C1-C4-haloalkyl, C1-C4-haloalkoxy, C1-C4-alkylthio,
or their environmentally compatible salts.
Preferred compounds of the formula Ib are compiled in the table which follows:
Very especially preferred are the compounds
4-[2-chloro-3-(4,5-dihydroisoxazol-3-yl)-4-methylsulfonylbenzoyl]-1-methyl-5-hydroxy-1H-pyrazole,
4-[2-methyl-3-(4,5-dihydroisoxazol-3-yl) -4-methylsulfonylbenzoyl ]-1-methyl-5-hydroxy-1H-pyrazole,
4-[2-chloro-3-(3-methylisoxazol-5-yl)-4-methylsulfonylbenzoyl]-1-methyl-5-hydroxy-1H-pyrazole,
or their environmentally compatible salts.
Suitable environmentally compatible salts are salts of, for example, alkali metals, alkaline earth metals, ammonia or amines.
Suitable nitrogenous fertilizers b) are ammonia and ammonium salts, urea, thiourea and mixtures of these.
Examples of suitable fertilizers are aqueous ammonia solution, ammonium nitrate, ammonium sulfate, ammonium hydrogen sulfate, ammonium chloride, ammonium acetate, ammonium formate, ammonium oxalate, ammonium carbonate, ammonium hydrogen carbonate, ammonium nitrate, ammonium thiosulfate, ammonium phosphate, ammonium hydrogen diphosphate, ammonium dihydrogen monophosphate, ammonium sodium hydrogen phosphate, ammonium thiocyanate, urea and thiourea, and mixtures of these, and also ammonium nitrate/urea solutions (UAN or AHL solutions).
Preferred nitrogenous fertilizers are urea, ammonium nitrate, ammonium nitrate/urea solutions, ammonium sulfate, ammonium phosphate, ammonium hydrogen diphosphate, ammonium dihydrogen monophosphate and ammonium sodium hydrogen phosphate.
Very especially preferred are urea, ammonium nitrate and ammonium nitrate/urea solutions. The ammonium nitrate/urea solutions preferably have a total nitrogen content of 28-33% (w/w) and are commercially available from BASF, for example under the brand name Ensol(copyright) 28.
Suitable adjuvants c) are vegetable oils which can be partially hydrogenated and hydrogenated, modified vegetable oils, mineral oils, alcohol alkoxylates, alcohol ethoxylates, alkylated EO/PO block copolymers, alkylphenol ethoxylates, polyols, EO/PO block copolymers, organosilicon compounds, alkylglycosides, alkyl polyglycosides, alkyl sulfates, sulfated alcohol alkoxylates, alkylarylsulfonates, alkylsulfonates, dialkylsulfosuccinates, phosphated alcohol alkoxylates, fatty amine alkoxylates, esters, carboxylates, ester ethoxylates, dialkyl adipates, dicarboxylic acid derivatives, such as alkenylsuccinic anhydride condensates with polyalkylene oxides or polyhydroxyamines; dialkyl phthalates, ethoxylated sorbitan esters of natural fatty acids and ethoxylated glycerides of natural fatty acids.
Preferred adjuvants are alcohol alkoxylates, such as alkyl ethers of EO/PO copolymers, for example Plurafac(copyright) (BASF AG), Synperionic(copyright) LF (ICI), alcohol ethoxylates, the alcohol being a C8-C18-alcohol of synthetic or natural origin which may be either linear or branched. The ethoxylate moiety contains on average 3-20 moles of ethylene oxide, depending on the alcohol used. Products used are, for example, Lutensol(copyright) ON, TO, AO and A by BASF, alkylarylsulfonates, such as nonylphenyl ethoxylates with 5-15 moles of EO, polyols such as polyethylene glycol or polypropylene glycol, EO/PO block copolymers such as, for example, Pluronic(copyright) PE (BASF AG) or Synperionic(copyright) PE (ICI), organosilicon compounds, alkyl polyglycosides, such as, for example, Agrimul(copyright) (Henkel KGA), AG 6202 (Akzo-Nobel), Atplus(copyright) 450 (ICI) or Lutensol(copyright) GD 70 (BASF AG), fatty amine alkoxylates, such as, for example, Ethomeen(copyright) and Armobleem(copyright) by Akzo Nobel, esters of natural and synthetic fatty acids, such as, for example, methyl oleates or methyl cocoates, dialkyl adipates, ethoxylated sorbitan esters of natural fatty acids, such as, for example, Tween(copyright) by ICI Surfactants (Tween(copyright) 20, Tween(copyright) 85, Tween(copyright) 80), ethoxylated glycerides of natural fatty acids, such as, for example, Glycerox(copyright) by Croda.
Other examples are found in:
McCutcheon""s; Emulsifiers and Detergents, Volume 1: Emulsifiers and Detergents 1994 North American Edition;
McCutcheon""s Division, Glen Rock N.J., USA,
McCutcheon""s; Emulsifiers and Detergents, Volume 2: Emulsifiers and Detergents 1994 International Edition;
McCutcheon Division, Glen Rock N.J., USA,
Surfactants in Europe;
A Directory of surface active agents available in Europe 2nd Ed. 1989;
Terg Data, Darlington, England,
Ash, Michael;
Handbook of cosmetic and personal care additives 1994;
Gower Publishing Ltd, Aldershot, England
Ash, Michael;
Handbook of industrial Surfactants 1993;
Gower Publishing Ltd. Aldershot, England.
The herbicidal mixture according to the invention comprises the following amounts of the components a) to c):
0.5 to 90% by weight of the 3-heterocyclyl-substituted benzoyl derivative a);
5 to 94.5% by weight of the nitrogenous fertilizer b);
5 to 50% by weight of the adjuvant c).
Preferred weight ratios are:
0.5 to 50% by weight of the 3-heterocyclyl-substituted benzoyl derivative a);
5 to 90% by weight of the nitrogenous fertilizer b);
5 to 50% by weight of the adjuvant c).
The components together add up to 100% by weight.
The individual components a) to c) of the herbicidal mixture according to the invention can be formulated and packaged jointly or individually. Furthermore, it is possible to formulate and pack the components a) together with b), or a) together with c).
The practitioner uses the herbicidal mixture or its individual components for use in the spray tank.
For this purpose, the herbicidal mixture is diluted with water, adding, if appropriate, other auxiliaries and additives. However, the practitioner may also mix the individual components a) to c) of the herbicidal mixture according to the invention himself in the spray tank and, if appropriate, add further auxiliaries and additives (tank mix method).
For the tank mix method, the components a) to c) are mixed in the spray tank and made up to the desired use concentration with water.
The following adjuvants have proved advantageous for the tank mix method:
mineral oils, liquid paraffins, vegetable oils, hydrogenated or methylated vegetable oils, such as, for example, soya oil, rapeseed oil, sunflower oil, esters and salts of natural carboxylic acids, such as, for example, methyl oleate, methylated seed oils, nonionic surfactants, such as ethoxylated alcohols, ethoxylated phenols, fatty amine ethoxylates, and mixtures of these.
Further auxiliaries and additives may be added for better processing. The following components have proved themselves as auxiliaries and additives:
solvents, antifoams, buffers, thickeners, spreading agents, compatibility-enhancing agents.
Examples and brands of adjuvants, auxiliaries and additives are described in Farm Chemicals Handbook 1997; Meister Publishing 1997 p. C10 xe2x80x9cadjuvantxe2x80x9d or 1998 Weed Control Manual p. 86.
The mixture according to the invention is suitable as herbicide. The herbicidal mixture effects very good control of vegetation on non-crop areas, especially at high rates of application. In crops such as wheat, rice, maize, soybeans and cotton it acts against broad-leaved weeds and grass weeds without damaging the crop plants substantially. This effect is observed especially at low rates of application.
Depending on the application method in question the herbicidal mixture can additionally be employed in a further number of crop plants for eliminating undesirable plants. Examples of suitable crops are the following:
Allium cepa, Ananas comosus, Arachis hypogaea, Asparagus officinalis, Beta vulgaris spec. altissima, Beta vulgaris spec. rapa, Brassica napus var. napus, Brassica napus var. napobrassica, Brassica rapa var. silvestris, Camellia sinensis, Carthamus tinctorius, Carya illinoinensis, Citrus limon, Citrus sinensis, Coffea arabica (Coffea canephora, Coffea liberica), Cucumis sativus, Cynodon dactylon, Daucus carota, Elaeis guineensis, Fragaria vesca, Glycine max, Gossypium hirsutum, (Gossypium arboreum, Gossypium herbaceum, Gossypium vitifolium), Helianthus annuus, Hevea brasiliensis, Hordeum vulgare, Humulus lupulus, Ipomoea batatas, Juglans regia, Lens culinaris, Linum usitatissimum, Lycopersicon lycopersicum, Malus spec., Manihot esculenta, Medicago sativa, Musa spec., Nicotiana tabacum (N.rustica), Olea europaea, Oryza sativa, Phaseolus lunatus, Phaseolus vulgaris, Picea abies, Pinus spec., Pisum sativum, Prunus avium, Prunus persica, Pyrus communis, Ribes sylvestre, Ricinus communis, Saccharum officinarum, Secale cereale, Solanum tuberosum, Sorghum bicolor (s. vulgare), Theobroma cacao, Trifolium pratense, Triticum aestivum, Triticum durum, Vicia faba, Vitis vinifera and Zea mays. 
Moreover, the herbicidal mixture can also be used in crops which tolerate the action of herbicides due to breeding including genetic engineering methods.
The herbicidal mixture can be applied pre- or post-emergence. If the herbicidal mixture is less well tolerated by certain crop plants, application techniques may be used in which the herbidical mixture is sprayed, with the aid of the spray apparatus, in such a way that it comes into little contact, if any, with the leaves of the sensitive crop plants while reaching the leaves of undesirable plants which grow underneath, or the bare soil (post-directed, lay-by).
The herbicidal mixture can be employed, for example, in the form of directly sprayable aqueous solutions, powders, suspensions, also highly-concentrated aqueous, oily or other suspensions or dispersions, emulsions, oil dispersions, pastes, dusts, materials for spreading or granules, by means of spraying, atomizing, dusting, spreading or pouring. The use forms depend on the intended purposes; in any case, they should guarantee the finest possible distribution of the herbicidal mixture according to the invention.
Suitable inert auxiliaries are essentially: mineral oil fractions of medium to high boiling point such as kerosene and diesel oil, furthermore coal tar oils and oils of vegetable or animal origin, aliphatic, cyclic and aromatic hydrocarbons, e.g. paraffin, tetrahydronaphthalene, alkylated naphthalenes and their derivatives, alkylated benzenes and their derivatives, alcohols such as methanol, ethanol, propanol, butanol and cyclohexanol, ketones such as cyclohexanone, or strongly polar solvents, e.g. amines such as N-methylpyrrolidone and water.
Aqueous use forms can be prepared from emulsion concentrates, suspensions, pastes, wettable powders or water-dispersible granules by adding water. To prepare emulsions, pastes or oil dispersions, the herbicidal mixture, as such or dissolved in an oil or solvent, can be homogenized in water by means of wetting agent, tackifier, dispersant or emulsifier. However, it is also possible to prepare concentrates composed of active substance, wetting agent, tackifier, dispersant or emulsifier and, if appropriate, solvent or oil, and these concentrates are suitable for dilution with water.
Suitable surfactants are the alkali metal, alkaline earth metal and ammonium salts of aromatic sulfonic acids, e.g. lignosulfonic acid, phenolsulfonic acid, naphthalenesulfonic acid and dibutylnaphthalenesulfonic acid, and of fatty acids, of alkyl- and alkylarylsulfonates, of alkyl sulfates, lauryl ether sulfates and fatty alcohol sulfates, and salts of sulfated hexa-, hepta- and octadecanols, and of fatty alcohol glycol ether, condensates of sulfonated naphthalene and its derivatives with formaldehyde, condensates of naphthalene, or of the naphthalenesulfonic acids, with phenol and formaldehyde, polyoxyethylene octylphenyl ether, ethoxylated isooctyl-, octyl- or nonylphenol, alkylphenyl and tributylphenyl polyglycol ethers, alkylaryl polyether alcohols, isotridecyl alcohol, fatty alcohol/ethylene oxide condensates, ethoxylated castor oil, polyoxyethylene alkyl ethers or polyoxypropylene alkyl ethers, lauryl alcohol polyglycol ether acetate, sorbitol esters, lignin-sulfite waste liquors or methylcellulose.
Powders, materials for spreading and dusts can be prepared by mixing or concomitantly grinding the herbicidal mixture with a solid carrier.
Granules, e.g. coated granules, impregnated granules and homogeneous granules, can be prepared by binding the active ingredients to solid carriers. Solid carriers are mineral earths such as silicas, silica gels, silicates, talc, kaolin, limestone, lime, chalk, bole, loess, clay, dolomite, diatomaceous earth, calcium sulfate, magnesium sulfate, magnesium oxide, ground synthetic materials, fertilizers such as ammonium sulfate, ammonium phosphate, ammonium nitrate, ureas and products of vegetable origin such as cereal meal, tree bark meal, wood meal and nutshell meal, cellulose powder or other solid carriers.
The concentrations of the herbicidal mixture in the ready-to-use products can be varied within wide ranges. In general, the formulations comprise approximately from 0.001 to 98% by weight, preferably 0.01 to 95% by weight, of the herbicidal mixture. The components of the mixture are employed in a purity of from 90% to 100%, preferably 95% to 100% (according to NMR spectrum).